JP2003041146A - New cobalt phthalocyanine and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain cobalt phthalocyanine providing stronger reddish blue having a smaller λmax. SOLUTION: This cobalt phthalocyanine has diffraction peaks at Bragg angle (2θ±0.2 deg.)=4.8 deg., 8.5 deg. and 9.8 deg. measured by CuKα-line in a powder X-ray diffraction pattern. This method for producing the specific cobalt phthalocyanine comprises reacting phthalic acid and/or its derivative with pyromellitic acid and/or its derivative, cobalt and/or its compound and urea and/or ammonia in the presence of a catalyst in a sulfur-containing organic solvent in a pressurized state.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel crystalline cobalt phthalocyanine and a method for producing the same, and moreover, a fine cobalt phthalocyanine which can be used as it is as a coloring agent for resins, varnishes, plastics and the like can be obtained by a synthetic reaction step only. It relates to a method of manufacturing in stages.

[0002]

2. Description of the Related Art Phthalocyanine pigments are blue and
It is a blue pigment with a clear hue and great coloring power and excellent in various resistance such as weather resistance, heat resistance and chemical resistance.
It is widely used as a coloring material for various substances, starting from existing fields such as plastics, to advanced fields such as optical materials and electrophotographic materials.

By the way, cobalt phthalocyanine has several crystal types. α-type cobalt phthalocyanine is
Black angle 2θ is 6.8, 7.4, 10.1, 15.
6, 16.3, 24.2, 24.9, 25.3, 26.
It has a diffraction peak at 9, 27.9 °, while β-type cobalt phthalocyanine has a black angle 2θ of 7.0, 9.2, 10.6, 12.6, 18.2, 1
8.5, 23.9, 26.3, 28.1 and 30.5 °
It has a diffraction peak at.

[0004]

However, in the above-mentioned existing crystal type cobalt phthalocyanine, the light ray wavelength (λmax) at which the light transmittance is maximum is in the relatively long wavelength side of about 473 nm. In recent years, with the advancement of required performance of optical materials and electrophotographic materials, there is a demand for cobalt phthalocyanine having a shorter wavelength λmax, that is, a stronger reddish blue color.

[0005]

The inventors of the present invention have made diligent studies in view of the above circumstances, and have produced cobalt phthalocyanine in the same manner as various production methods known for copper phthalocyanine. It has been found that, in the case of a specific production method, a novel crystal type cobalt phthalocyanine different from the conventional one can be obtained. The inventors have found that the novel crystalline cobalt phthalocyanine has a smaller λmax than the conventional α-type or β-type cobalt phthalocyanine, that is, a stronger reddish blue color, and completed the present invention.

That is, according to the present invention, the Bragg angle (2θ ± 0.2 °) in the powder X-ray diffraction pattern measured by CuKα ray
A cobalt phthalocyanine having diffraction peaks at 4.8 °, 8.5 °, and 9.8 ° (hereinafter referred to as a novel crystalline cobalt phthalocyanine) is provided.

The novel crystalline cobalt phthalocyanine of the present invention comprises, for example, phthalic acid and / or its derivative,
It can be produced by a method in which pyromellitic acid and / or its derivative, cobalt and / or its compound, and urea and / or ammonia are reacted under pressure in a sulfur-containing organic solvent in the presence of a catalyst. .

According to this method, a cheaper raw material can be used, and cobalt phthalocyanine can be produced more simply as a reaction operation.

The phthalic acid derivative which can be used in the production method of the present invention includes alkali metal phthalate, copper phthalate, ammonium phthalate, phthalic anhydride, phthalimide, phthalamide, phthalamic acid and its salts or esters, phthalic acid. Examples thereof include acid esters and phthalonitrile.

Examples of pyromellitic acid derivatives include alkali metal pyromellitic acid, copper pyromellitic acid, ammonium pyromellitic acid, pyromellitic dianhydride, pyromellitic imide, pyromellitic acid ester, and 4,5-dicyanophthalimide. Etc. can be mentioned. The amount of pyromellitic acid and / or its derivative used is 20 to 0.2 relative to 80 to 99.8 mol% of phthalic acid and / or its derivative.
The molar ratio is preferably in the range of 10 to 0.5 mol% with respect to 90 to 99.5 mol% of phthalic acid and / or its derivative in view of excellent hue clarity, chemical resistance, transparency and economy.
Is particularly preferred.

In the present invention, a third phthalic acid-substituted derivative other than phthalic acid and / or a derivative thereof and pyromellitic acid and / or a derivative thereof can be used, and the color tone and various characteristics of the cobalt phthalocyanine produced thereby can be used. Can be changed.

Examples of such substances include alkali metal trimellitic acid salts, copper trimellitic acid salts, ammonium trimellitic acid salts, trimellitic anhydride, trimellitic imides and trimellitic acid esters.

Examples of cobalt compounds include cobalt halides, oxides, hydroxides, sulfates, nitrates, acetates, etc. In the case of obtaining a novel crystalline cobalt phthalocyanine in a higher yield, It is preferable to use an anhydride (a substance that does not contain water of crystallization). The amount of phthalocyanine ring forming compound 4 is stoichiometrically determined.
It is 1 mol per mol.

The amount of urea and / or ammonia used is usually 4 to 26 mol in terms of ammonia per 4 mol of the phthalocyanine ring-forming compound, but when phthalonitrile is used, it may be a relatively small amount. When using an acid, a relatively large amount is required.

As the catalyst that can be used in the production method of the present invention, any of various known catalysts can be used, but molybdenum compounds such as molybdenum oxide and ammonium molybdate are particularly preferable. The amount used is generally 0.01 to 0.04 equivalent per 4 mol of the phthalocyanine ring forming compound.

In the production method of the present invention, it is preferable to use a reaction aid in combination with the catalyst, since the new crystalline cobalt phthalocyanine can be obtained in a higher yield.

Examples of the reaction aid include ammonium chloride, ammonium sulfate, ammonium acetate, etc. Among them, ammonium chloride is preferable. The amount of the reaction aid used is usually 0.1 to 4 mol per 4 mol of the phthalocyanine ring forming compound.

Examples of the sulfur-containing organic solvent used as the solvent include sulfolane, sulfolene, dimethyl sulfoxide and the like, and it is also possible to use a mixture thereof. Of these, sulfolane is most preferably used in consideration of various physical properties.

In the production method of the present invention, the reaction needs to be carried out under pressure, but this may be a self-generated pressure due to ammonia or carbon dioxide gas generated as the reaction proceeds. The magnitude of the pressure is preferably 0.1 to 10 MPa because the reaction can be completed without controlling the phthalocyanine forming reaction, which is a condensation reaction by dehydration and deammonification.

After the completion of the reaction, filtration, drying, pulverization, classification, purification, if necessary, are carried out so that the intended use form and quality are obtained.
Operations such as pigmentation can be performed.

After completion of the reaction based on the above-mentioned production method, cobalt phthalocyanine can be separated from the obtained reaction mixture by a filter such as Nutsche or filter press and used as a wet cake. Also,
It can also be dried and used as a dry powder. On the other hand, it is also possible to obtain a dry powder of cobalt phthalocyanine from the reaction mixture obtained after the completion of the reaction by using a vacuum desolventizer such as an evaporator or a rotary vacuum dryer.

In the powder X-ray diffraction pattern, the cobalt phthalocyanine thus obtained by the production method of the present invention is, as described above, Bragg angle (2θ ± 0.2 °) = 4.8 °, 8.
It has new diffraction peaks at 5 ° and 9.8 °.

It should be noted that α-type and β-type cobalt phthalocyanine are known, and the spectrum diagrams such as mass spectrometry spectrum, infrared absorption spectrum and nuclear magnetic resonance spectrum are the same as those of the novel crystalline cobalt phthalocyanine of the present invention. Become. From this, it is possible to identify cobalt phthalocyanine except for the crystal form.

The powder X-ray diffraction pattern for identifying the crystal form of cobalt phthalocyanine is based on CuKα ray (wavelength 0.154) according to JISK 0131 (general rule of X-ray diffraction analysis).
It is determined by X-ray diffraction measurement at 1 nanometer).
In this powder X-ray diffraction pattern, the specific diffraction peak of the specific crystal type cobalt phthalocyanine shows the specific Bragg angle (2
It appears at the position of θ ± 0.2 °).

The effect of the present invention is exhibited to some extent by the specific crystal type cobalt phthalocyanine, whether it is a crude pigment or a pigment obtained by post-treating (pigmenting) the crude pigment.

According to the production method of the present invention, finer cobalt phthalocyanine than that obtained by the conventional production method can be obtained, and cobalt phthalocyanine having a quality as a pigment can be obtained without so-called pigmentation.

In the production method of the present invention, if necessary, a small amount of cobalt phthalocyanine having a sulfonic acid group or a carboxylic acid group (referred to as cobalt phthalocyanine derivative) or the like can be added or formed in the optional step. .

When the cobalt phthalocyanine obtained by the production method of the present invention has a relatively large particle diameter or when it is desired to further reduce the particle diameter, it can be crushed before use.

If necessary, the crude pigment of the specific crystal form cobalt phthalocyanine can be prepared by subjecting it to a known pigment such as a solvent salt milling method or a solvent method, without changing the crystal form. It is also possible to improve dispersibility, coloring power and the like.

When the use of the novel crystalline cobalt phthalocyanine of the present invention is in the advanced fields such as optical materials and electrophotographic materials, the wet cake and dry powder of cobalt phthalocyanine are neutral, By washing with acidic or alkaline hot water or water, for example, 1 to 10 times, the content of free cobalt, the concentration of free anion, etc. are substantially reduced to a level at which there is no problem in the required performance in the final application. It is preferable because it can be reduced and the improvement of characteristics in the final use can be expected.

The thus-obtained cobalt phthalocyanine is mixed and dispersed in various thermoplastic resins, thermosetting resins or active energy ray-curable resins, and molded or applied to a substrate and cured if necessary to give a printed matter or a colored resin. It is possible to obtain a molded product, a coated product in which the base material is coated with a colored resin film, and the like.

[0032]

EXAMPLES The present invention will now be specifically described with reference to examples. Hereinafter, "parts" and "%" are based on mass unless otherwise specified.

Example 1 84.2 parts of phthalic anhydride, 2.6 parts of pyromellitic dianhydride, 149.5 parts of urea, 23.2 parts of anhydrous cobalt sulfate, ammonium molybdate.
3 parts, 7.7 parts ammonium chloride and 30 sulfolane
Charge 0 part into a pressure resistant reactor and heat while stirring to 20
The temperature was raised to 0 ° C and kept at 200 ° C for 2 hours. After starting heating, the internal pressure gradually rises to 0.3 MPa at an internal temperature of 110 ° C.
Reached After that, the generated gas was appropriately discharged to the outside of the reaction vessel to keep the internal pressure at 0.3 MPa. After completion of the reaction, sulfolane was filtered, the residue was added to 2500 parts of 1% hydrochloric acid, and the mixture was stirred at about 70 ° C. for 1 hour and then suction filtered. The cake was thoroughly washed with hot water at 70 ° C. and then dried to obtain cobalt phthalocyanine.

The X-ray diffraction of this product was measured by Rigaku Denki Co., Ltd.
Using INT1100, tube: Cu, sampling angle: 0.020 °, scan speed: 4.00 ° / m
FIG. 1 shows the result of measurement under the conditions of in and operating angle 2θ / θ. As you can see, the black angle 2θ is 4.8,
It had diffraction peaks at 8.5 and 9.8 °.

The infrared absorption spectrum was measured based on the powder KBr method. The result is shown in FIG. This had a spectrum similar to that of a known β-type cobalt phthalocyanine described later.

When the size of the particles was observed with a transmission electron microscope, the particles were extremely fine needle-like crystals with a length of about 0.05 μm.

[Comparative Example 1] The same procedure as in Example 1 was repeated except that the reaction solvent was replaced with Hysol P (a sulfur-free organic solvent manufactured by Nippon Petrochemical Co., Ltd.) without using pyromellitic dianhydride. , Β-type cobalt phthalocyanine was obtained. As a result of measuring the X-ray diffraction of this product, the black angle 2θ was 7.0, 9.2, 10.6, 12.6, 18.2, 1
It had diffraction peaks at 8.5, 23.9, 26.3, 28.1 and 30.5 °.

Comparative Example 2 The β-type cobalt phthalocyanine obtained in Comparative Example 1 was treated with an acid paste to form α.
Converted to type cobalt phthalocyanine. As a result of measuring X-ray diffraction of this product, the black angle 2θ was 6.8, 7.
4, 10.1, 15.6, 16.3, 24.2, 24.
It had diffraction peaks at 9, 25.3, 26.9 and 27.9 °.

The size of each cobalt phthalocyanine particle of Comparative Examples 1 and 2 was observed with a transmission electron microscope.
All were extremely fine crystals with a length of about 0.05 μm.

[Reference Example] Using a paint conditioner, 1.5 parts of each cobalt phthalocyanine obtained in Example 1 and Comparative Examples 1 and 2 was uniformly dispersed in 100 parts of melamine-alkyd resin for paint. A blue paint was prepared. The colored film produced from each of these paints is
The wavelength (λmax) at which the transmittance of the spectral transmission spectrum at 380 to 780 nm is maximum was measured using a first-class spectrophotometer (spectrophotometer) specified in Z 8722. In addition, a baseline process is performed to correct the transmittance of the resin itself. The brightness was visually evaluated. The results are shown in Table 1.

[0041]

[Table 1] Table 1

As can be seen from Table 1, the novel crystalline cobalt phthalocyanine of the present invention has the maximum transmittance on the shorter wavelength side as compared with the conventional α-type or β-type cobalt phthalocyanine. It can be used as a reddish blue colorant. Also, because the brightness is excellent,
It can be seen that it also has the advantage that the light attenuation during light transmission is smaller. Therefore, the novel crystalline cobalt phthalocyanine of the present invention is useful in advanced fields such as optical materials, liquid crystal display materials and electrophotographic materials.

It can be seen that the novel crystalline cobalt phthalocyanine of the present invention is extremely excellent as a coloring material for forming the blue part of a transmission type color filter particularly in the field of liquid crystal display materials.

[0044]

EFFECTS OF THE INVENTION The novel crystalline cobalt phthalocyanine of the present invention has a wavelength at which the maximum transmittance is shorter than that of the conventional cobalt phthalocyanine, and is characterized in that it has a stronger reddish color. It is also useful as a coloring material in advanced fields such as optical materials, liquid crystal display materials, and electrophotographic materials, as well as general-purpose fields such as printing inks, paints, and colored resin molded products. Further, according to the production method of the present invention, a new crystalline cobalt phthalocyanine can be obtained in a high yield, and since it has a fine particle size,
A particularly remarkable effect that cobalt phthalocyanine having quality as a pigment can be produced in a single step without going through a pigmenting step is exerted.

[Brief description of drawings]

FIG. 1 is a powder X-ray diffraction pattern of the novel crystalline cobalt phthalocyanine of the present invention.

FIG. 2 is an infrared absorption spectrum diagram of the novel crystalline cobalt phthalocyanine of the present invention.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroshi Katsube             3-14-17 Nakazato, Kita-ku, Tokyo (72) Inventor Junko Sunouchi             3-9809-9 Doihoncho, Hasaki Town, Kashima District, Ibaraki Prefecture

Claims (2)

[Claims] 1. A Bragg angle (2θ ± 0.2 °) = 4.8 ° in a powder X-ray diffraction pattern measured by CuKα ray.
Cobalt phthalocyanine having diffraction peaks at 8.5 ° and 9.8 °. 2. Phthalic acid and / or its derivative, pyromellitic acid and / or its derivative, cobalt and / or its compound, and urea and / or ammonia in the presence of a catalyst in a sulfur-containing organic solvent, Bragg angle (2θ ± 0.2 °) in powder X-ray diffraction pattern measured by CuKα ray characterized by reacting under pressure
= A method for producing cobalt phthalocyanine having diffraction peaks at 4.8 °, 8.5 ° and 9.8 °.